Quantifying spin contamination in algebraic diagrammatic construction theory of electronic excitations.

Algebraic diagrammatic construction (ADC) is a computationally efficient approach for simulating excited electronic states, absorption spectra, and electron correlation. Due to their origin in perturbation theory, the single-reference ADC methods may be susceptible to spin contamination when applied to molecules with unpaired electrons. In this work, we develop an approach to quantify spin contamination in the ADC calculations of electronic excitations and apply it to a variety of open-shell molecules starting with either the unrestricted (UHF) or restricted open-shell (ROHF) Hartree–Fock reference wavefunctions. Our results show that the accuracy of low-order ADC approximations [ADC(2) and ADC(3)] significantly decreases when the UHF reference spin contamination exceeds 0.05 a.u. Such strongly spin-contaminated molecules exhibit severe excited-state spin symmetry breaking that contributes to decreasing the quality of computed excitation energies and oscillator strengths. In a case study of phenyl radical, we demonstrate that spin contamination can significantly affect the simulated UV/Vis spectra, altering the relative energies, intensities, and order of electronic transitions. The results presented here motivate the development of spin-adapted ADC methods for open-shell molecules. [ABSTRACT FROM AUTHOR]